EP1029885A1 - Procédé de préparation de composés organosiliciques - Google Patents

Procédé de préparation de composés organosiliciques Download PDF

Info

Publication number
EP1029885A1
EP1029885A1 EP99123670A EP99123670A EP1029885A1 EP 1029885 A1 EP1029885 A1 EP 1029885A1 EP 99123670 A EP99123670 A EP 99123670A EP 99123670 A EP99123670 A EP 99123670A EP 1029885 A1 EP1029885 A1 EP 1029885A1
Authority
EP
European Patent Office
Prior art keywords
organosilicon compound
alkoxy
group
functional
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP99123670A
Other languages
German (de)
English (en)
Other versions
EP1029885B1 (fr
Inventor
Satoshi Dow Corning Toray Sil.Co. Ltd. Onodera
Makoto Dow Corning Toray sil.Co. Ltd. Yoshitake
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DuPont Toray Specialty Materials KK
Original Assignee
Dow Corning Toray Silicone Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dow Corning Toray Silicone Co Ltd filed Critical Dow Corning Toray Silicone Co Ltd
Publication of EP1029885A1 publication Critical patent/EP1029885A1/fr
Application granted granted Critical
Publication of EP1029885B1 publication Critical patent/EP1029885B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0834—Compounds having one or more O-Si linkage
    • C07F7/0838—Compounds with one or more Si-O-Si sequences
    • C07F7/0872—Preparation and treatment thereof
    • C07F7/0876—Reactions involving the formation of bonds to a Si atom of a Si-O-Si sequence other than a bond of the Si-O-Si linkage
    • C07F7/0878—Si-C bond
    • C07F7/0879—Hydrosilylation reactions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0834—Compounds having one or more O-Si linkage
    • C07F7/0838—Compounds with one or more Si-O-Si sequences
    • C07F7/0872—Preparation and treatment thereof
    • C07F7/0874—Reactions involving a bond of the Si-O-Si linkage
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C08G77/485—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms containing less than 25 silicon atoms

Definitions

  • This invention relates to a method for the preparation of organosilicon compounds. More particularly, this invention relates to a method for preparing organosilicon compounds that can convert the Si-bonded alkoxy group in organosilicon compounds to the diorganosilyl group at high conversion ratios. The invention additionally relates to a method for synthesizing carbosiloxane dendrimers using said preparative method.
  • Japanese Patent Application Hei 10-29297 (29,297/1998) teaches the reaction of alkoxysilane and 1,1,3,3-tetramethyldisiloxane in the presence of a carboxylic acid and a perfluoroalkanesulfonic acid.
  • the former method suffers from a low conversion in the dimethylsilylation reaction, resulting in the presence of a fair amount of residual alkoxy in the organosilicon compound product.
  • the latter method does provide a high conversion in the dimethylsilylation reaction, but cannot give the target product in high yields due to the occurrence of secondary reactions.
  • These methods have thus been unable to produce SiH-functional organosilicon compounds in high purities from Si-bonded alkoxy-functional organosilicon compounds.
  • An object of the invention is to provide a method for preparing organosilicon compounds that can convert the Si-bonded alkoxy group to the diorganosilyl group at high conversion ratios and that can do so without the occurrence of secondary reactions.
  • Another object of the invention is to provide a method for preparing a high-purity carbosiloxane dendrimer with a narrow molecular weight distribution through the use of the preceding method.
  • This invention relates to a method for preparing organosilicon compounds.
  • Said method is characterized by converting the Si-bonded alkoxy in an Si-bonded alkoxy-functional organosilicon compound to a diorganosilyl group by reacting the Si-bonded alkoxy-functional organosilicon compound with an organodisiloxane having Si-bonded hydrogen atoms in an alcohol-containing acidic aqueous solution and subsequently treating with a sulfonic acid catalyst and carboxylic acid.
  • Figure 1 contains the 29 Si-nuclear magnetic resonance spectrogram of the carbosiloxane dendrimer synthesized in Example 1.
  • Figure 2 contains the 29 Si-nuclear magnetic resonance spectrogram of the carbosiloxane dendrimer synthesized in Comparative Example 1.
  • Figure 3 contains the 29 Si-nuclear magnetic resonance spectrogram of the organosilicon compound synthesized in Comparative Example 2.
  • Figure 4 contains the 29 Si-nuclear magnetic resonance spectrogram of the organosilicon compound synthesized in Example 2.
  • This invention relates to a method for preparing organosilicon compounds.
  • the Si-bonded alkoxy-functional organosilicon compound is exemplified by alkoxysilanes, organoalkoxysilanes, alkoxy-functional organosiloxane oligomers, alkoxy-functional organopolysiloxanes, and alkoxy-functional carbosiloxane dendrimers.
  • the alkoxy group is exemplified by methoxy, ethoxy, propoxy, and butoxy, among which methoxy and ethoxy are preferred.
  • the alkoxysilanes are exemplified by tetraalkoxysilanes such as tetramethoxysilane and tetraethoxysilane; organotrialkoxysilanes such as trimethoxysilane, triethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane; diorganodialkoxysilanes such as dimethyldimethoxysilane, dimethyldiethoxysilane, vinylmethyldimethoxysilane, phenylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, and 3-mercaptopropylmethyldimethoxysilane; and organomonoalkoxysilanes such as tri
  • the alkoxy-functional organosiloxane oligomers are exemplified by the partial hydrolysis and condensation products of the above alkoxysilanes and also by 1-methoxy-1,1,3,3,5,5,7,7-octamethyltetrasiloxane, 1-methoxy-nonamethyltetrasiloxane, and 1-methoxy-7-vinyloctamethyltetrasiloxane.
  • the carbosiloxane dendrimer encompassed by this invention is a polymer with a highly branched structure in which the siloxane bond and silalkylene bond alternate and in which the core is a siloxane unit with the general formula X 1 R 3 a SiO (3-a)/2 .
  • R 3 is a monovalent organic group, for example, C 1 to C 10 alkyl, aryl, haloalkyl, ether-containing groups, and ester-containing groups.
  • the subscript a is an integer from 0 to 2.
  • This alkoxy-functional carbosiloxane dendrimer is exemplified by polymers with the following average molecular formulas.
  • the alkoxy-functional carbosiloxane dendrimer can be synthesized by an addition reaction between an SiH-functional organosilicon compound and an alkenyltrialkoxysilane in the presence of a platinum transition metal catalyst.
  • the SiH-functional organosilicon compound is exemplified by the compounds having the following average molecular formulas. and wherein R 1 represents C 1 to C 10 monovalent hydrocarbyl, R 2 represents monovalent organic groups, the subscripts have the following values: l is an integer from 0 to 3, m is an integer with a value of at least 3, n is an integer with a value of at least 0, p is an integer with a value of at least 2, and q and r are both integers with values of at least 4.
  • the monovalent hydrocarbyl R 1 is exemplified by alkyl such as methyl, ethyl, and propyl; alkenyl such as vinyl, allyl, butenyl, and hexenyl; aryl such as phenyl, tolyl, and xylyl; and aralkyl such as benzyl and phenethyl. Methyl is preferred for R 1 .
  • the monovalent organic group R 2 is exemplified by C 1 to C 10 alkyl, aryl, haloalkyl, ether-containing groups, and ester-containing groups.
  • the alkenyltrialkoxysilane is exemplified by the general formula R 7 Si(OR 5 ) 3 , in which R 5 represents C 1 to C 10 alkyl and R 7 represents C 2 to C 10 alkenyl.
  • the platinum transition metal catalyst is exemplified by chloroplatinic acid, alcohol-modified chloroplatinic acid, olefin complexes of platinum, and platinum/diketonate complexes.
  • R 1 in the organodisiloxane HR 1 2 Si-O-SiR 1 2 H represents C 1 to C 10 monovalent hydrocarbyl, for example, alkyl such as methyl, ethyl, and propyl; alkenyl such as vinyl, allyl, butenyl, and hexenyl; aryl such as phenyl, tolyl, and xylyl; and aralkyl such as benzyl and phenethyl. Methyl is preferred for R 1 .
  • the alcohol-containing acidic aqueous solution preferably the 2:1:2 (weight) mixture of alcohol : acid : water.
  • the alcohol is exemplified by methanol, ethanol, n-propanol, and isopropanol.
  • the acid is exemplified by concentrated hydrochloric acid, sulfuric acid, carboxylic acids, and sulfonic acids.
  • the carboxylic acid is exemplified by formic acid, acetic acid, propionic acid, benzoic acid, and substituted benzoic acids.
  • Formic acid and acetic are preferred for their ability to provide a good acceleration of the diorganosilylation reaction.
  • the sulfonic acid catalyst is a catalyst that accelerates the diorganosilylation reaction.
  • this component are sulfuric acid and perfluoroalkanesulfonic acids such as trifluoromethanesulfonic acid.
  • the preparative method of this invention commences with the diorganosilylation in alcohol-containing acidic aqueous solution of the Si-bonded alkoxy by the organodisiloxane HR 1 2 Si-O-SiR 1 2 H. More specifically, a liquid mixture is prepared from the alcohol-containing acidic aqueous solution and the organodisiloxane using the latter in an amount corresponding to at least 1.0 equivalent and preferably at least 1.2 equivalents with reference to the alkoxy in the Si-bonded alkoxy-functional organosilicon compound.
  • the Si-bonded alkoxy-functional organosilicon compound is then added dropwise to this liquid mixture at from 0 to 80°C, preferably 10 to 50°C, and more preferably 20 to 40°C, to effect conversion of the alkoxy to diorganosilyl.
  • a sulfonic acid catalyst and carboxylic acid are added to the organosilicon compound product, and the residual alkoxy is converted to diorganosilyl at from 0 to 80°C, preferably 40 to 70°C, and more preferably 45 to 55°C.
  • the carboxylic acid will be used in this stage generally in an amount corresponding to at least 0.6 equivalent and preferably in an amount corresponding to at least 1.0 equivalent with reference to the alkoxy present in the Si-bonded alkoxy-functional organosilicon compound prior to the rcaction.
  • the addition of the sulfonic acid catalyst should be at least 200 ppm with reference to the reaction mixture and is preferably at least 500 ppm and more preferably at least 1,000 ppm.
  • a water removal operation may be run between the two stages of this diorganosilylation reaction. After completion of the reaction, work up by a water wash, neutralization, drying, and concentration under reduced pressure will produce a very pure organosilicon compound in which the alkoxy groups previously present in the molecule have all been converted to diorganosilyl.
  • the preparative method of the invention can be used to synthesize a highly branched carbosiloxane dendrimer in which the siloxane bond and silalkylene bond occur in alternation. This is accomplished through the repetitive and alternating execution of
  • One advantage offered by the preparative method described above is that it produces a high-purity SiH-functional organosilicon compound. This advantage accrues because the method can convert all the Si-bonded alkoxy in the molecule to diorganosilyl and can do so without the occurrence of secondary reactions such as, for example, siloxane bond rearrangement.
  • the preparative method of this invention is extremely effective when the starting Si-bonded alkoxy-functional organosilicon compound has been synthesized using a platinum transition metal catalyst.
  • the SiH-functional organosilicon compound afforded by this preparative method is not subject to dehydrogenation of its Si-bonded hydrogen by the platinum transition metal catalyst.
  • the combination of the diorganosilylation reaction of this invention with an addition reaction with alkenyltrialkoxysilane can produce a high-purity carbosiloxane dendrimer with a narrow molecular weight distribution whose molecular weight, determined on a polystyrene basis, has a dispersity index (the ratio Mw/Mn between the weight-average molecular weight Mw and the number-average molecular weight Mn) no greater than 2.
  • a dispersity index the ratio Mw/Mn between the weight-average molecular weight Mw and the number-average molecular weight Mn
  • Me indicates the methyl group.
  • the carbosiloxane dendrimers were identified by 29 Si-nuclear magnetic resonance analysis and gel permeation chromatography (solvent: toluene).
  • reaction solution was subsequently transferred to a separatory funnel, the lower layer was separated off, and the remaining upper layer was washed 3 times with 200 mL water and dried over calcium chloride. After filtration of the resulting solids, 210 g acetic acid and 0.86 mg trifluoromethanesulfonic acid were added and the temperature was raised to 50°C and a reaction was carried out for 1 hour.
  • reaction solution was transferred to a separatory runnel. This was followed by separating off the lower layer, washing 3 times with 200 mL water and once with 200 mL saturated aqueous sodium carbonate solution, and drying over calcium chloride. The resulting solids were filtered off and the reaction solution was then concentrated under reduced pressure to give 342.4 g of a colorless and transparent liquid.
  • reaction solution was subsequently transferred to a separatory funnel, the lower layer was separated off, and the remaining upper layer was washed 3 times with 500 mL water and once with 500 mL saturated aqueous sodium carbonate solution and was dried over calcium chloride. Filtration of the resulting solids and concentration of the reaction solution under reduced pressure then gave 1,085 g of a colorless and transparent liquid.
  • reaction solution was transferred to a separatory funnel, the lower layer was separated off, and the remaining upper layer was washed 3 times with 20 mL water and once with 20 mL saturated aqueous sodium carbonate solution and was dried over calcium chloride. Filtration of the resulting solids and concentration of the reaction solution under reduced pressure then gave 109 g of a colorless and transparent liquid.
  • this liquid was analyzed by gel permeation chromatography, its molecular weight distribution did not present a single, monodisperse peak, but rather was divided into a number of peaks. Overall, these results indicated that the reaction product contained by-products and that the target carbosiloxane dendrimer with the average molecular formula had not been obtained in high purity. According to gel permeation chromatography this organosilicon compound had a number-average molecular weight (polystyrene basis) of 920 and a dispersity index of 1.84.
  • reaction solution was then transferred to a separatory funnel and the lower layer was separated off. The remaining upper layer was washed 3 times with 30 mL water and dried over calcium chloride. After filtering off the resulting solids, 110.1 g acetic acid was added, the temperature was raised to 50°C, and 66.7 mg trifluoromethanesulfonic acid was added. The reaction solution was then reacted for 7 hours.
  • reaction solution was transferred to a separatory funnel and the lower layer was separated off followed by washing 3 times with 30 mL water and once with 30 mL saturated aqueous sodium carbonate solution and drying over calcium chloride. Filtering off the resulting solids and concentration of the reaction solution under reduced pressure gave 167.5 g of a colorless and transparent liquid.
  • this liquid by 29 Si-nuclear magnetic resonance analysis confirmed it to be the organosilicon compound having the following average molecular formula and containing an average of 3 silicon-bonded hydrogen atoms in the molecule. According to gel permeation chromatography, this organosilicon compound had a number-average molecular weight (polystyrene basis) of 424 and a dispersity index of 1.02.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Silicon Polymers (AREA)
EP99123670A 1999-01-27 1999-11-29 Procédé de préparation de composés organosiliciques Expired - Lifetime EP1029885B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP1870499 1999-01-27
JP01870499A JP3999902B2 (ja) 1999-01-27 1999-01-27 有機ケイ素化合物の製造方法

Publications (2)

Publication Number Publication Date
EP1029885A1 true EP1029885A1 (fr) 2000-08-23
EP1029885B1 EP1029885B1 (fr) 2003-05-21

Family

ID=11979042

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99123670A Expired - Lifetime EP1029885B1 (fr) 1999-01-27 1999-11-29 Procédé de préparation de composés organosiliciques

Country Status (6)

Country Link
US (1) US6147243A (fr)
EP (1) EP1029885B1 (fr)
JP (1) JP3999902B2 (fr)
KR (1) KR20000052395A (fr)
CA (1) CA2291205A1 (fr)
DE (1) DE69908080T2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2464286C1 (ru) * 2011-03-09 2012-10-20 Федеральное государственное унитарное предприятие "Государственный ордена Трудового Красного Знамени научно-исследовательский институт химии и технологии элементоорганических соединений" (ФГУП ГНИИХТЭОС) Способ получения термостойких олигоорганосилоксановых смол

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4187974B2 (ja) * 2002-01-31 2008-11-26 東レ・ダウコーニング株式会社 シリコーン化合物の製造方法
US8722153B2 (en) * 2007-05-25 2014-05-13 Dow Corning Corporation Release coating composition and method of forming the same
WO2010141432A1 (fr) 2009-06-02 2010-12-09 Rogers Corporation Sous-ensembles de circuits thermoconducteurs, leur procédé de fabrication et articles formés à partir de ces sous-ensembles
KR102584736B1 (ko) 2018-10-02 2023-10-05 로저스코포레이션 코팅된 질화 붕소를 포함하는 인쇄회로기판 서브스트레이트
CN111440320A (zh) * 2020-04-01 2020-07-24 中科院广州化学有限公司 一种防雾添加剂及其制备方法与应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0195936A1 (fr) * 1985-02-22 1986-10-01 Toray Silicone Company Limited Procédé de préparation de polyorganosiloxanes et les polymères préparés par ce procédé
EP0291871A2 (fr) * 1987-05-15 1988-11-23 Wacker-Chemie GmbH Procédé de préparation d'organopolysiloxanes et organopolysiloxane pouvant être obtenue par ce procédé
JPH10292047A (ja) * 1997-04-21 1998-11-04 Toray Dow Corning Silicone Co Ltd シロキサン化合物の製造方法
EP0939098A2 (fr) * 1998-02-25 1999-09-01 Dow Corning Toray Silicone Company, Ltd. Copolymère ramifié de siloxane-silalkylène

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06792B2 (ja) * 1989-12-27 1994-01-05 信越化学工業株式会社 水素シロキサンの製造方法
US5446185A (en) * 1994-11-14 1995-08-29 Dow Corning Corporation Alkylhydrido siloxanes

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0195936A1 (fr) * 1985-02-22 1986-10-01 Toray Silicone Company Limited Procédé de préparation de polyorganosiloxanes et les polymères préparés par ce procédé
EP0291871A2 (fr) * 1987-05-15 1988-11-23 Wacker-Chemie GmbH Procédé de préparation d'organopolysiloxanes et organopolysiloxane pouvant être obtenue par ce procédé
JPH10292047A (ja) * 1997-04-21 1998-11-04 Toray Dow Corning Silicone Co Ltd シロキサン化合物の製造方法
EP0939098A2 (fr) * 1998-02-25 1999-09-01 Dow Corning Toray Silicone Company, Ltd. Copolymère ramifié de siloxane-silalkylène

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 1999, no. 02 26 February 1999 (1999-02-26) *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2464286C1 (ru) * 2011-03-09 2012-10-20 Федеральное государственное унитарное предприятие "Государственный ордена Трудового Красного Знамени научно-исследовательский институт химии и технологии элементоорганических соединений" (ФГУП ГНИИХТЭОС) Способ получения термостойких олигоорганосилоксановых смол

Also Published As

Publication number Publication date
DE69908080D1 (de) 2003-06-26
US6147243A (en) 2000-11-14
EP1029885B1 (fr) 2003-05-21
JP3999902B2 (ja) 2007-10-31
DE69908080T2 (de) 2003-12-18
KR20000052395A (ko) 2000-08-25
JP2000212283A (ja) 2000-08-02
CA2291205A1 (fr) 2000-05-30

Similar Documents

Publication Publication Date Title
KR100574573B1 (ko) 카보실록산 덴드리머
US5395955A (en) Method for the preparation of carbinol group-containing organopolysiloxane
JP2538426B2 (ja) オルガノポリシロキサンの製造方法
EP1472264B1 (fr) Procedes de preparation de composes de silicium
EP0962482B1 (fr) Dendrimères de carbosiloxane
JP3015139B2 (ja) オルガノポリシロキサンおよびその製造方法
EP1029885B1 (fr) Procédé de préparation de composés organosiliciques
EP1675671A2 (fr) Synthese facile d'anions polyedres de silsesquioxane, et leur utilisation
EP1031592A2 (fr) Dendrimères carbosiloxanes
JPH10298288A (ja) 分岐状シロキサン・シルアルキレン共重合体
JP3756576B2 (ja) ヒドロキシフェニル基含有ポリオルガノシロキサン
JP3349735B2 (ja) ヒドロシリル化法
JPH0632902A (ja) 分子鎖末端に水酸基を有する直鎖状オルガノポリシロキサンの製造方法
EP0967216B1 (fr) Procédé pour la préparation de siloxanes
EP0939098B1 (fr) Copolymère ramifié de siloxane-silalkylène
US5290841A (en) Organocyclosiloxane and method for its preparation
US5929187A (en) Branched siloxane-silalkylene copolymer
RU2389735C2 (ru) (органоалкоксисилил)олигоалкилгидридсилоксаны и способ их получения
US5239085A (en) Organocyclosiloxane and method for its preparation
CN115678012B (zh) 一种多端烯烃基支化聚硅氧烷及其制备方法和应用
JP2000212283A5 (fr)
KR100507886B1 (ko) 분지상실록산-실알킬렌공중합체
WO2007007598A1 (fr) Résine d’organosilicone possédant des groupes hydroxyle alcoolique et son procédé de production
JP3015153B2 (ja) フェニル基含有オルガノポリシロキサンの製造方法
JP3257414B2 (ja) 環状エーテル基を有するオルガノポリシロキサン

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): DE FR GB IT NL

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

17P Request for examination filed

Effective date: 20010126

AKX Designation fees paid

Free format text: DE FR GB IT NL

17Q First examination report despatched

Effective date: 20010913

RIC1 Information provided on ipc code assigned before grant

Free format text: 7C 08G 77/06 A, 7C 08G 77/48 B, 7C 07F 7/08 B

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Designated state(s): DE FR GB IT NL

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REF Corresponds to:

Ref document number: 69908080

Country of ref document: DE

Date of ref document: 20030626

Kind code of ref document: P

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20031129

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20040224

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20040601

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20040602

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20031129

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20040601

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20051129

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20031130

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20111021